JP2012530665A - Method for increasing luminous efficiency of field emission luminescent material, luminescent glass element and preparation method thereof - Google Patents
Method for increasing luminous efficiency of field emission luminescent material, luminescent glass element and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 180
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 120
- 239000002184 metal Substances 0.000 claims abstract description 120
- 239000000758 substrate Substances 0.000 claims abstract description 87
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 26
- 239000004332 silver Substances 0.000 claims description 26
- 229910052709 silver Inorganic materials 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- 229910052737 gold Inorganic materials 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000007740 vapor deposition Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- -1 alkali metal salts Chemical class 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005498 polishing Methods 0.000 description 19
- 238000005566 electron beam evaporation Methods 0.000 description 12
- 238000000295 emission spectrum Methods 0.000 description 10
- 230000005284 excitation Effects 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 4
- 230000001808 coupling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003502 terbium compounds Chemical class 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J63/00—Cathode-ray or electron-stream lamps
- H01J63/06—Lamps with luminescent screen excited by the ray or stream
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/77742—Silicates
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/77—Coatings having a rough surface
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Abstract
本発明では電界放出発光材料の発光効率を高める方法、発光ガラス素子およびその調製方法を開示しており、化学式がａＭ２Ｏ・ｂＹ２Ｏ３・ｃＳｉＯ２・ｄＴｂ２Ｏ３である発光ガラスを基板として、基板の表面に非周期性の金属マイクロ・ナノ構造を持つ金属層を形成するものであり、金属層に陰極線を出射すると、陰極線は金属層を透過した後、基板を励起して発光させる。調製方法では、発光ガラス基板を調製して、ガラス基板の表面に金属層を形成した後、アニール処理し、冷却した後に発光ガラス素子が得られる、工程を含む。本発明の発光ガラス素子は工程が簡単で、使用しやすく信頼性が高く、電界放出発光材料の発光効率を大幅に高める方法、優れた透光性、高い均一性を備え、発光効率が高く、安定性に優れ、構造が簡単で、調製方法が簡単で、低コストの発光ガラス素子を提供する。
【選択図】図１How to increase the luminous efficiency of the field emission light-emitting material in the present invention, discloses a light-emitting glass element and its preparation method, the light-emitting glass formula is aM 2 O · bY 2 O 3 · cSiO 2 · dTb 2 O 3 As a substrate, a metal layer having an aperiodic metal micro / nano structure is formed on the surface of the substrate. When a cathode ray is emitted to the metal layer, the cathode ray passes through the metal layer and then excites the substrate to emit light. Let The preparation method includes a step of preparing a luminescent glass substrate, forming a metal layer on the surface of the glass substrate, annealing, and cooling to obtain a luminescent glass element. The light-emitting glass element of the present invention has a simple process, is easy to use, has high reliability, has a method of greatly increasing the light emission efficiency of the field emission light-emitting material, has excellent translucency, and high uniformity, has high light emission efficiency, Provided is a light-emitting glass element having excellent stability, a simple structure, a simple preparation method, and low cost.
[Selection] Figure 1
Description
本発明は発光材料の技術分野に属するものであり、電界放出発光材料の発光効率を高める方法、発光ガラス素子およびその調製方法に関し、とりわけ電界放出発光材料の発光効率を高める方法、発光ガラス素子およびその調製方法に関する。 The present invention belongs to the technical field of luminescent materials, and relates to a method for increasing the luminous efficiency of a field emission luminescent material, a luminescent glass element and a method for preparing the same, and in particular, a method for increasing the luminescent efficiency of a field emission luminescent material, a luminescent glass element and It relates to the preparation method.
現在、真空マイクロエレクトロニクス分野において、電界放出デバイスは照明およびディスプレイ分野において幅広い応用の将来性を示しており、国内外の研究機関から広く注目を集めている。その動作原理は次の通りである。真空環境下で、陽極により電界放出陰極アレイ（ｆｉｅｌｄ ｅｍｉｓｓｉｖｅ ａｒｒａｙｓ,ＦＥＡｓ）に正電圧を印加することで加速電界を形成し、陰極放出された電子が加速して陰極板上の発光材料にぶつかり発光する。電界放出デバイスの動作温度範囲は広く（−４０℃〜８０℃）、反応時間は短く（−１ｍｓ）、構造が簡単で、消費電力が少なく、エコロジーで環境保護に適合する。一部蛍光粉体、発光ガラス、発光フィルムなどの材料は電界放出デバイスにて発光材料として使用することができるものの、これらはいずれも発光効率が低いという本質的な問題があり、電界放出デバイスの応用、特に照明分野での応用への制限が大きい。 Currently, in the field of vacuum microelectronics, field emission devices have shown wide-ranging application potential in the fields of illumination and display, and are attracting widespread attention from domestic and foreign research institutions. The operation principle is as follows. Under a vacuum environment, an accelerating electric field is formed by applying a positive voltage to field emission cathode arrays (FEAs) by the anode, and the electrons emitted from the cathode are accelerated and collide with the light emitting material on the cathode plate. To do. The field emission device has a wide operating temperature range (−40 ° C. to 80 ° C.), a short reaction time (−1 ms), a simple structure, low power consumption, ecology and environmental protection. Although some materials such as fluorescent powder, luminescent glass, and luminescent film can be used as luminescent materials in field emission devices, they all have the inherent problem of low luminous efficiency. There are significant restrictions on applications, especially in the lighting field.
表面プラズモン（Ｓｕｒｆａｃｅ Ｐｌａｓｍｏｎ，ＳＰ）は金属および媒体の界面を伝搬する一種の波であり、その振幅は界面から離れるにつれて指数が減衰する。金属表面の構造を改変すると、表面プラズモンポラリトン（Ｓｕｒｆａｃｅ Ｐｌａｓｍｏｎ Ｐｏｌａｒｉｔｏｎｓ，ＳＰＰｓ）の性質、色の分散関係、励起モード、カップリング効果などに大きな変化が生じる。ＳＰＰｓによる磁場は、光波のサブ波長のサイズ構造中で伝搬するうえ、光周波数からマイクロ波帯域の電磁放射を発生して調節して、光伝搬に対する能動的な制御が実現する。ＳＰＰｓの励起では、光の状態密度を高めて、自然放出割合が向上するので、内部量子効率を大幅に高めて、現在における各種固体発光装置を発光効率が低いという苦境から開放して、新型の超高輝度および高速動作する発光デバイスの誕生を促す。 Surface plasmon (SP) is a kind of wave that propagates through the interface between metal and medium, and the amplitude of the surface plasmon decreases as the distance from the interface increases. If the structure of the metal surface is modified, a large change occurs in the properties of surface plasmon polaritons (SPPs), color dispersion relations, excitation modes, coupling effects, and the like. The magnetic field generated by the SPPs propagates in the size structure of the subwavelength of the light wave, and generates and adjusts electromagnetic radiation in the microwave band from the optical frequency to realize active control over the light propagation. In the excitation of SPPs, the density of states of light is increased and the spontaneous emission ratio is improved, so that the internal quantum efficiency is greatly increased, and various solid state light emitting devices are released from the predicament of low luminous efficiency. Encourage the birth of light-emitting devices that operate at ultra-high brightness and high speed.
本発明が解決すべき技術的課題は、従来技術は発光効率が低いという欠陥に対して、工程が簡単で、使用しやすく信頼性が高く、電界放出発光材料の発光効率を大幅に高める方法を提供するところにある。 The technical problem to be solved by the present invention is a method for greatly improving the luminous efficiency of a field emission light-emitting material, which is simple in process, easy to use and highly reliable against the defect that the conventional technique has low luminous efficiency. There is to offer.
本発明がさらに解決すべき技術的課題は、優れた透光性、高い均一性を備え、発光効率が高く、安定性に優れ、構造が簡単な電界放出発光材料の発光効率を大幅に高める方法に用いられる発光ガラス素子を提供するところにある。 The technical problem to be further solved by the present invention is a method for greatly increasing the light emission efficiency of a field emission light emitting material having excellent light transmission, high uniformity, high light emission efficiency, excellent stability and simple structure. The present invention provides a light emitting glass element used in the above.
本発明のまたさらに解決すべき技術的課題は、工程が簡単で、低コストの発光ガラス素子の調製方法を提供するところにある。 A further technical problem to be solved by the present invention is to provide a method for preparing a light-emitting glass element having a simple process and a low cost.
本発明がその技術的課題を解決するために採用する技術的思想は以下のとおりである。電界放出発光材料の発光効率を高める方法であって、発光ガラスを基板として、金属材料が当該発光ガラス基板の表面に非周期性の金属マイクロ・ナノ構造を持つ金属層を形成することで、発光ガラス素子を得る工程を含み、そして当該発光ガラス基板に陰極線を出射すると、当該陰極線は前記金属層を透過した後、前記発光ガラス基板を励起して発光させる The technical idea that the present invention adopts in order to solve the technical problem is as follows. A method for increasing the luminous efficiency of a field emission light-emitting material, in which a light-emitting glass is used as a substrate, and a metal material forms a metal layer having a non-periodic metal micro / nano structure on the surface of the light-emitting glass substrate. A step of obtaining a glass element, and emitting a cathode ray to the light emitting glass substrate, the cathode ray passes through the metal layer and then excites the light emitting glass substrate to emit light.
ものであり、前記発光ガラス基板の化学式はａＭ２Ｏ・ｂＹ２Ｏ３・ｃＳｉＯ２・ｄＴｂ２Ｏ３であって、式中、Ｍはアルカリ金属元素であり、ａ、ｂ、ｃ、ｄはモル分率であり、これらの値の範囲が、ａは２５〜６０、ｂは０．０１〜１５、ｃは４０〜７０、ｄは０．０１〜１５である。 Is intended, the chemical formula of the emission glass substrate is a aM 2 O · bY 2 O 3 · cSiO 2 · dTb 2 O 3, wherein, M is an alkali metal element, a, b, c, d is These are molar fractions, and the ranges of these values are: a is 25 to 60, b is 0.01 to 15, c is 40 to 70, and d is 0.01 to 15.
発光ガラス基板を備えた電界放出発光材料の発光効率を高める方法に用いられる発光ガラス素子であって、前記発光ガラス基板の表面には金属層が設けられており、前記金属層は金属微細構造を有しており、前記発光ガラス基板は、化学式ａＭ２Ｏ・ｂＹ２Ｏ３・ｃＳｉＯ２・ｄＴｂ２Ｏ３の複合酸化物を含み、
式中、Ｍはアルカリ金属元素であり、ａ、ｂ、ｃ、ｄはモル分率であり、これらの値の範囲が、ａは２５〜６０、ｂは０．０１〜１５、ｃは４０〜７０、ｄは０．０１〜１５である。
A light-emitting glass element used in a method for increasing luminous efficiency of a field emission light-emitting material provided with a light-emitting glass substrate, wherein a metal layer is provided on a surface of the light-emitting glass substrate, and the metal layer has a metal microstructure. has, the light emitting glass substrate includes a composite oxide of formula aM 2 O · bY 2 O 3 · cSiO 2 · dTb 2 O 3,
In the formula, M is an alkali metal element, a, b, c, and d are mole fractions, and the ranges of these values are as follows: a is 25 to 60, b is 0.01 to 15, and c is 40 to 40. 70 and d are 0.01-15.
前記発光ガラス素子において、前記アルカリ金属元素はＮａ、Ｋ、Ｌｉのうちの少なくとも一種類である。 In the light emitting glass element, the alkali metal element is at least one of Na, K, and Li.
前記発光ガラス素子において、前記金属層の金属は金、銀、アルミニウム、銅、チタン、鉄、ニッケル、コバルト、クロム、パラジウム、マグネシウム、亜鉛のうちの少なくとも一種類である。 In the luminescent glass element, the metal of the metal layer is at least one of gold, silver, aluminum, copper, titanium, iron, nickel, cobalt, chromium, palladium, magnesium, and zinc.
前記発光ガラス素子において、前記金属層の金属が金、銀、アルミニウムのうちの少なくとも一種類である。 In the light-emitting glass element, the metal of the metal layer is at least one of gold, silver, and aluminum.
前記発光ガラス素子において、前記金属層の厚さが０．５ｎｍ〜２００ｎｍである。 In the light-emitting glass element, the metal layer has a thickness of 0.5 nm to 200 nm.
前記発光ガラス素子において、前記金属層の厚さが１ｎｍ〜１００ｎｍである。 In the light emitting glass element, the metal layer has a thickness of 1 nm to 100 nm.
発光ガラス素子の調製方法であって、
化学式がａＭ２Ｏ・ｂＹ２Ｏ３・ｃＳｉＯ２・ｄＴｂ２Ｏ３であって、式中、Ｍはアルカリ金属元素であり、ａ、ｂ、ｃ、ｄはモル分率であり、これらの値の範囲が、ａは２５〜６０、ｂは０．０１〜１５、ｃは４０〜７０、ｄは０．０１〜１５である複合酸化物を含む発光ガラス基板を調製する工程と、
前記発光ガラス基板の表面に金属層を形成する工程と、
前記発光ガラス基板および金属層を真空にてアニール処理して、前記金属層に金属微細構造を形成して、冷却した後に所望の発光ガラス素子を得る工程と、を含む。
A method for preparing a light emitting glass element, comprising:
Formula is a aM 2 O · bY 2 O 3 · cSiO 2 · dTb 2 O 3, wherein, M is an alkali metal element, a, b, c, d are mole fractions, these values Wherein a is 25 to 60, b is 0.01 to 15, c is 40 to 70, and d is 0.01 to 15;
Forming a metal layer on the surface of the light emitting glass substrate;
Annealing the luminescent glass substrate and the metal layer in a vacuum to form a metal microstructure in the metal layer and cooling to obtain a desired luminescent glass element.
前記発光ガラス素子の調製方法において、前記発光ガラス基板の調製工程は、各々がモル分率に対応するアルカリ金属塩、ＳｉＯ２、Ｙ２Ｏ３およびＴｂ４Ｏ７原料を得て、１２００℃〜１５００℃の温度で混合・溶融、冷却して、さらに還元雰囲気中にて、６００〜１１００℃の温度でアニール処理し、発光ガラス基板を得る。 In the method for preparing the light-emitting glass element, the step of preparing the light-emitting glass substrate includes obtaining alkali metal salts, SiO 2 , Y 2 O 3 and Tb 4 O 7 raw materials each corresponding to a molar fraction of 1200 ° C. to Mixing, melting, and cooling are performed at a temperature of 1500 ° C., and further annealing is performed at a temperature of 600 to 1100 ° C. in a reducing atmosphere to obtain a light emitting glass substrate.
前記発光ガラス素子の調製方法において、前記金属層は金属スパッタリングまたは蒸着により発光ガラス基板表面に形成されたものである。 In the method for preparing the light emitting glass element, the metal layer is formed on the surface of the light emitting glass substrate by metal sputtering or vapor deposition.
前記発光ガラス素子の調製方法において、前記真空アニール処理は５０℃〜６５０℃で行われ、アニール時間は５分間〜５時間である。 In the method for preparing the light emitting glass element, the vacuum annealing treatment is performed at 50 ° C. to 650 ° C., and the annealing time is 5 minutes to 5 hours.
前記発光ガラス素子の調製方法において、前記真空アニール処理は１００℃〜５００℃で行われるのが好ましく、アニール時間は１５分間〜３時間であるのが好ましい。 In the method for preparing a light emitting glass element, the vacuum annealing treatment is preferably performed at 100 ° C. to 500 ° C., and the annealing time is preferably 15 minutes to 3 hours.
本発明では、化学式がａＭ２Ｏ・ｂＹ２Ｏ３・ｃＳｉＯ２・ｄＴｂ２Ｏ３である発光ガラス上に金属層を一層設けており、当該金属層は陰極線下にて発光ガラスとの間の界面に表面プラズモンが形成され、表面プラズモン現象により、化学式がａＭ２Ｏ・ｂＹ２Ｏ３・ｃＳｉＯ２・ｄＴｂ２Ｏ３である発光ガラスの発光効率を高めており、当該方法により電界放出発光材料は発光効率が低いという問題を解決している。 In the present invention, the chemical formula aM 2 O · bY are further provided a metal layer 2 O 3 · cSiO 2 · dTb 2 O 3 a is emitting the glass, the metal layer between the light emitting glass in cathode ray under surface plasmon formed at the interface, the surface plasmon phenomenon, the formula has enhanced emission efficiency of the light-emitting glass is aM 2 O · bY 2 O 3 · cSiO 2 · dTb 2 O 3, the field emission light emitting material by the method Solves the problem of low luminous efficiency.
本発明の発光ガラス素子は金属層と、発光ガラスとからなり、発光ガラスは化学式がａＭ２Ｏ・ｂＹ２Ｏ３・ｃＳｉＯ２・ｄＴｂ２Ｏ３である緑色発光ガラスであって、金属層は非周期性の金属マイクロ・ナノ構造を持ち、出射された陰極線はまず金属層を透過して、ひいては発光ガラスを励起して発光させるものであり、この過程において、金属層と発光ガラスとの界面上に表面プラズモン現象が発生しており、当該表面プラズモン現象により発光ガラスの内部量子効率が大幅に高められ、つまり自然放出割合が向上して、ひいては発光ガラスの発光効率を大幅に高めるので、電界放出発光材料は発光効率が低いという問題を解決している。 Emitting glass element of the present invention is a metal layer made of a light-emitting glass, luminescent glass is a green light-emitting glass formula is aM 2 O · bY 2 O 3 · cSiO 2 · dTb 2 O 3, metal layer The cathode wire that has a non-periodic metal micro / nano structure is first transmitted through the metal layer, and thus excites the luminescent glass to emit light. In this process, the interface between the metal layer and the luminescent glass A surface plasmon phenomenon has occurred on the surface, and the surface plasmon phenomenon significantly increases the internal quantum efficiency of the luminescent glass, that is, the spontaneous emission ratio is improved, and as a result, the luminous efficiency of the luminescent glass is greatly increased. The emitted light emitting material solves the problem of low luminous efficiency.
さらに、本発明の発光ガラス素子の調製方法は、発光ガラス基板上に金属層を一層形成して、その後アニール処理を経るだけで、所望の発光ガラス素子を得ることができるので、工程が簡単で、低コストで、幅広い応用の将来性を備える。 Furthermore, the method for preparing the light-emitting glass element of the present invention is simple because the desired light-emitting glass element can be obtained simply by forming a metal layer on the light-emitting glass substrate and then performing an annealing process. , Low cost, with broad application potential.
本発明の目的、技術的思想および長所をより明確にするために、図面および実施例を合わせて、本発明により詳細な説明を行う。理解されるべきは、ここに記述する具体的な実施例は本発明を解釈するためだけのものであり、本発明の限定に用いるものではないということである。 In order to clarify the object, technical idea and advantages of the present invention, the present invention will be described in detail with reference to the drawings and examples. It should be understood that the specific embodiments described herein are only for interpreting the invention and are not intended to limit the invention.
電界放出発光材料の発光効率を高める方法は、具体的に以下の工程を含む。発光ガラスを基板として、金属材料を発光ガラス基板の表面にスパッタリングして、非周期性の金属マイクロ・ナノ構造を持つ金属層を形成することで、発光ガラス素子を得るものであり、当該発光ガラス基板に陰極線を出射すると、当該陰極線は前記金属層を透過した後、前記発光ガラス基板を励起して発光させる。前記金属材料は金、銀、アルミニウム、銅、チタン、鉄、ニッケル、コバルト、クロム、パラジウム、マグネシウム、亜鉛のうちの少なくとも一種類または複数種類であって、金、銀、アルミニウムのうちの一種類または複数種類であるのが好ましい。発光ガラス基板は緑色発光ガラスであり、当該緑色発光ガラスの化学式はａＭ２Ｏ・ｂＹ２Ｏ３・ｃＳｉＯ２・ｄＴｂ２Ｏ３であって、式中、ＭはＮａ、Ｋ、Ｌｉのうちの少なくとも一種類であり、ａ、ｂ、ｃ、ｄはモル分率であり、これらの値の範囲が、ａは２５〜６０、ｂは０．０１〜１５、ｃは４０〜７０、ｄは０．０１〜１５である。 The method for increasing the luminous efficiency of the field emission luminescent material specifically includes the following steps. A light emitting glass element is obtained by sputtering a metal material on the surface of a light emitting glass substrate using a light emitting glass as a substrate to form a metal layer having an aperiodic metal micro-nano structure. When a cathode ray is emitted to the substrate, the cathode ray passes through the metal layer and then excites the luminescent glass substrate to emit light. The metal material is at least one or more of gold, silver, aluminum, copper, titanium, iron, nickel, cobalt, chromium, palladium, magnesium, and zinc, and one of gold, silver, and aluminum Or it is preferable that there are multiple types. Emission glass substrate is green-emitting glass, the chemical formula of the green emission glass is a aM 2 O · bY 2 O 3 · cSiO 2 · dTb 2 O 3, wherein, M is Na, K, of Li At least one kind, a, b, c, and d are mole fractions, and these values range from 25 to 60, b from 0.01 to 15, c from 40 to 70, and d from 0. .01-15.
図１を参照する。上記した電界放出発光材料の発光効率を高める方法に用いられるガラス素子は、発光ガラス基板１と、発光ガラス基板１の表面に設けられる金属層２とを備えている。金属層２は金属微細構造を有しており、当該金属微細構造はときにはマイクロ・ナノ構造と呼ばれる。さらに、当該金属微細構造は非周期性、つまり不規則に配列された金属結晶体からなるものである Please refer to FIG. A glass element used in the above-described method for increasing the luminous efficiency of a field emission luminescent material includes a luminescent glass substrate 1 and a metal layer 2 provided on the surface of the luminescent glass substrate 1. The metal layer 2 has a metal microstructure, and the metal microstructure is sometimes called a micro / nano structure. Further, the metal microstructure is non-periodic, that is, composed of irregularly arranged metal crystals.
当該発光ガラス基板１は化学式ａＭ２Ｏ・ｂＹ２Ｏ３・ｃＳｉＯ２・ｄＴｂ２Ｏ３の複合酸化物を含み、式中、Ｍはアルカリ金属元素であり、ａ、ｂ、ｃ、ｄはモル分率であり、各々の値の範囲が、ａは２５〜６０、ｂは０．０１〜１５、ｃは４０〜７０、ｄは０．０１〜１５である。当該発光ガラス基板１中にはテルビウムの化合物が含まれており、当該テルビウムの化合物はこの種の組成の発光ガラスにてその発光効果を充分に発揮できる。当該発光ガラス基板１はさらに優れた透光性能を備えている。 The luminescent glass substrate 1 includes a composite oxide of formula aM 2 O · bY 2 O 3 · cSiO 2 · dTb 2 O 3, wherein, M is an alkali metal element, a, b, c, d are mole Each value ranges from 25 to 60, b from 0.01 to 15, c from 40 to 70, and d from 0.01 to 15. The luminescent glass substrate 1 contains a terbium compound, and the terbium compound can sufficiently exhibit its light-emitting effect in the luminescent glass having this kind of composition. The light emitting glass substrate 1 has further excellent light transmission performance.
このうち、金属層２は、例えば酸化腐食しにくい金属といった化学的に安定性に優れた金属、 別に常用される金属、金、銀、アルミニウム、チタン、鉄、ニッケル、コバルト、クロム、パラジウム、マグネシウム、亜鉛のうちの少なくとも一種類からなるものであるのが好ましく、金、銀、アルミニウムのうちの少なくとも一種類であるのがより好ましい。金属層２中の金属物の種類はこれらの単一金属または複合金属とすることができる。複合金属は上記した金属の二種類または二種以上の合金であって、例えば、金属層２は銀・アルミニウム合金層または金・アルミニウム合金層とすることができ、このうちの銀または金の重量割合は７０％以上であるのが好ましい。金属層１４の厚さは０．５ｎｍ〜２００ｎｍであるのが好ましく、１ｎｍ〜１００ｎｍであるのがより好ましい。 Among these, the metal layer 2 is a metal having excellent chemical stability, for example, a metal that is not easily oxidized and corroded, and another commonly used metal, gold, silver, aluminum, titanium, iron, nickel, cobalt, chromium, palladium, magnesium. , Zinc is preferable, and at least one of gold, silver, and aluminum is more preferable. The kind of metal in the metal layer 2 can be a single metal or a composite metal. The composite metal is an alloy of two or more kinds of the metals described above. For example, the metal layer 2 can be a silver / aluminum alloy layer or a gold / aluminum alloy layer, and the weight of silver or gold among these layers The proportion is preferably 70% or more. The thickness of the metal layer 14 is preferably 0.5 nm to 200 nm, and more preferably 1 nm to 100 nm.
アルカリ金属ＭはＮａ、Ｋ、Ｌｉのうちの少なくとも一種類であるのが好ましい。 The alkali metal M is preferably at least one of Na, K, and Li.
上記発光ガラス素子を発光素子とすることで、例えば、電界放出型ディスプレイ、電界放出型光源または大型の広告看板などといった超高輝度および高速動作の発光デバイスに広く応用することができる。電界放出型ディスプレイを例にとれば、陽極が電界放出陰極アレイに正方向の電圧を印加して加速電界を形成して、陰極が放出した電子は、金属層２に対して陰極線を放出して、微細構造を有する金属層２と発光ガラス基板１との間に表面プラズモンが形成され、表面プラズモン現象により、発光ガラス基板１の内部量子効率を大幅に高めるので、発光材料の発光効率が低いという問題を解決する。また、発光ガラス基板１表面には金属層が一層形成されており、金属層全体と発光ガラス基板との間に均一な界面が形成されて、発光の均一性を高めることができる。 By using the light-emitting glass element as a light-emitting element, for example, it can be widely applied to a light-emitting device with ultra-brightness and high-speed operation such as a field emission display, a field emission light source, or a large advertising billboard. Taking a field emission display as an example, the anode applies a positive voltage to the field emission cathode array to form an accelerating electric field, and the electrons emitted from the cathode emit cathode rays to the metal layer 2. The surface plasmon is formed between the metal layer 2 having a fine structure and the light emitting glass substrate 1, and the internal quantum efficiency of the light emitting glass substrate 1 is greatly increased by the surface plasmon phenomenon, so that the light emitting efficiency of the light emitting material is low. Solve a problem. Further, a single metal layer is formed on the surface of the light emitting glass substrate 1, and a uniform interface is formed between the entire metal layer and the light emitting glass substrate, so that the uniformity of light emission can be improved.
上記発光ガラス素子の調製方法は以下の工程を含む。 The method for preparing the light-emitting glass element includes the following steps.
発光ガラス基板の調製：分析試薬のアルカリ金属塩、ＳｉＯ２および９９．９９％のＹ２Ｏ３、Ｔｂ４Ｏ７を主原料として、化学式ａＭ２Ｏ・ｂＹ２Ｏ３・ｃＳｉＯ２・ｄＴｂ２Ｏ３中の各元素間のモル分率の割合に応じて、対応する原料を量り取り、１２００℃〜１５００℃で１〜５時間溶融させて、室温にまで冷却し、さらに還元雰囲気中に置き、６００〜１１００℃で１〜２０時間アニール処理して、緑色発光ガラス基板を得る。また、さらに当該発光ガラス基板を一定寸法にカッティング、研磨加工することで、所望の発光ガラス基板を得る。 Preparation of light-emitting glass substrate: alkali metal salts of analytical reagents, SiO 2 and 99.99% of Y 2 O 3, Tb 4 O 7 as a main raw material, chemical formula aM 2 O · bY 2 O 3 · cSiO 2 · dTb 2 Depending on the molar fraction ratio between each element in O 3 , the corresponding raw material is weighed, melted at 1200 ° C. to 1500 ° C. for 1 to 5 hours, cooled to room temperature, and further placed in a reducing atmosphere. Annealing treatment is performed at 600 to 1100 ° C. for 1 to 20 hours to obtain a green light emitting glass substrate. Further, the desired luminescent glass substrate is obtained by further cutting and polishing the luminescent glass substrate to a certain size.
当該発光ガラス基板の表面に金属層を形成する：当該金属層は金属スパッタリングまたは蒸着により発光ガラス基板の表面に形成されたものである。 A metal layer is formed on the surface of the light emitting glass substrate: The metal layer is formed on the surface of the light emitting glass substrate by metal sputtering or vapor deposition.
そして、前記発光ガラス基板および金属層を真空にてアニール処理して、前記金属層に金属微細構造を形成して、冷却した後に、５０℃〜６５０℃にて真空アニール処理するものであり、具体的には、発光ガラス基板の表面に金属層を形成した後、５０℃〜６５０℃で５分間〜５時間真空アニールし、その後自然に室温にまで冷却する。このうち、アニール温度は１００℃〜５００℃であるのが好ましく、アニール時間は１５分間から３時間であるのが好ましい。 Then, the light emitting glass substrate and the metal layer are annealed in vacuum to form a metal microstructure on the metal layer, and after cooling, vacuum annealing is performed at 50 ° C. to 650 ° C. Specifically, after forming a metal layer on the surface of the light emitting glass substrate, vacuum annealing is performed at 50 ° C. to 650 ° C. for 5 minutes to 5 hours, and then naturally cooled to room temperature. Among these, the annealing temperature is preferably 100 ° C. to 500 ° C., and the annealing time is preferably 15 minutes to 3 hours.
上記した構造に似て、金属層２は例えば酸化腐食しにくい金属といった化学的に安定性に優れた金属、 別に常用される金属、金、銀、アルミニウム、チタン、鉄、ニッケル、コバルト、クロム、パラジウム、マグネシウム、亜鉛のうちの少なくとも一種類からなるものであるのが好ましく、金、銀、アルミニウムのうちの少なくとも一種類の金属から形成されるのがより好ましい。金属層２の厚さは０．５ｎｍ〜２００ｎｍであるのが好ましく、１ｎｍ〜１００ｎｍであるのがより好ましい。アルカリ金属ＭはＮａ、Ｋ、Ｌｉのうちの少なくとも一種類であるのが好ましい。当該金属層は金属スパッタリングまたは蒸着により発光ガラス基板の表面に形成されたものである。発光ガラス基板の表面に金属層を形成した後、５０℃〜６５０℃で５分間〜５時間真空アニール処理し、その後自然に室温にまで冷却する。このうち、アニール温度は１００℃〜５００℃であるのが好ましく、アニール時間は１５分間から３時間であるのが好ましい。 Similar to the structure described above, the metal layer 2 has a chemically stable metal such as a metal that is difficult to oxidize and corrode, another commonly used metal, gold, silver, aluminum, titanium, iron, nickel, cobalt, chromium, It is preferably made of at least one of palladium, magnesium and zinc, and more preferably made of at least one metal of gold, silver and aluminum. The thickness of the metal layer 2 is preferably 0.5 nm to 200 nm, and more preferably 1 nm to 100 nm. The alkali metal M is preferably at least one of Na, K, and Li. The metal layer is formed on the surface of the light emitting glass substrate by metal sputtering or vapor deposition. After forming a metal layer on the surface of the light emitting glass substrate, vacuum annealing is performed at 50 ° C. to 650 ° C. for 5 minutes to 5 hours, and then naturally cooled to room temperature. Among these, the annealing temperature is preferably 100 ° C. to 500 ° C., and the annealing time is preferably 15 minutes to 3 hours.
発光ガラス素子は上記した各種構造および組成などの特徴を備えている。実際の応用において、例えば電界放出型ディスプレイまたは照明光源に用いたとき、真空環境下で、陽極が電界放出陰極アレイに正方向の電圧を印加して加速電界を形成して、陰極が陰極線を出射し、陰極線の励起の下、電子ビームはまず金属層２を透過して発光ガラス基板１を励起して発光させるが、この過程において、金属層２と発光ガラス基板１との界面上に表面プラズモン現象が発生しており、当該現象により発光ガラス基板の内部量子効率が大幅に高められ、つまり自然放出割合が向上して、ひいては発光ガラスの発光効率を大幅に高めている。 The light emitting glass element has the characteristics such as various structures and compositions described above. In actual applications, for example, when used in a field emission display or an illumination light source, in a vacuum environment, the anode applies a positive voltage to the field emission cathode array to form an accelerating electric field, and the cathode emits a cathode ray. Under the excitation of the cathode ray, the electron beam first passes through the metal layer 2 to excite the luminescent glass substrate 1 to emit light. In this process, the surface plasmon is formed on the interface between the metal layer 2 and the luminescent glass substrate 1. A phenomenon has occurred, and the internal quantum efficiency of the luminescent glass substrate is greatly increased by the phenomenon, that is, the spontaneous emission ratio is improved, and as a result, the luminescent efficiency of the luminescent glass is greatly increased.
表面プラズモン（Ｓｕｒｆａｃｅ Ｐｌａｓｍｏｎ，ＳＰ）は金属および媒体の界面を伝搬する一種の波であり、その振幅は界面から離れるにつれて指数が減衰する。金属表面の構造を改変すると、表面プラズモンポラリトン（Ｓｕｒｆａｃｅ Ｐｌａｓｍｏｎ Ｐｏｌａｒｉｔｏｎｓ，ＳＰＰｓ）の性質、色の分散関係、励起モード、カップリング効果などに大きな変化が生じる。ＳＰＰｓによる磁場は、光波のサブ波長のサイズ構造中で伝搬するうえ、光周波数からマイクロ波帯域の電磁放射を発生して調節して、光伝搬に対する能動的な制御が実現する。したがって本発明では、ＳＰＰｓの励起性能を利用して、発光ガラス基板の光の状態密度を高めて、自然放出割合が向上し、しかも表面プラズモンのカップリング効果を利用することで、発光ガラス基板が発光したとき、これとカップリング共振効果が発生するので、発光ガラス基板の内部量子効率を大幅に高めて、発光ガラス基板の発光効率を高めることができる。 Surface plasmon (SP) is a kind of wave that propagates through the interface between metal and medium, and the amplitude of the surface plasmon decreases as the distance from the interface increases. If the structure of the metal surface is modified, a large change occurs in the properties of surface plasmon polaritons (SPPs), color dispersion relations, excitation modes, coupling effects, and the like. The magnetic field generated by the SPPs propagates in the size structure of the subwavelength of the light wave, and generates and adjusts electromagnetic radiation in the microwave band from the optical frequency to realize active control over the light propagation. Therefore, in the present invention, the light emission density of the luminescent glass substrate is increased by utilizing the excitation performance of SPPs, the spontaneous emission ratio is improved, and the coupling effect of the surface plasmon is utilized, whereby the luminescent glass substrate is When light is emitted, a coupling resonance effect is generated, so that the internal quantum efficiency of the light emitting glass substrate can be significantly increased, and the light emission efficiency of the light emitting glass substrate can be increased.
以下、複数の実施例により、発光ガラス素子の異なる組成およびその調製方法、およびその性能などを例示して説明する。 Hereinafter, different examples of the luminescent glass element, its preparation method, its performance, and the like will be described by way of examples.
実施例１
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる３０Ｌｉ２Ｏ・６Ｙ２Ｏ３・６０ＳｉＯ２・４Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し（各酸化物の前の数字はモル分率を表している。以下同じ）、マグネトロンスパッタリング装置でその表面に厚さ２ｎｍの金属銀層を堆積させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、３００℃の温度で３０分間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。図１に示すように、これは発光ガラス素子の構造図であって、本実施例における発光ガラス素子は発光ガラス基板１を基板として、その上に金属層が設けられており、本発明では金属銀層２を選択し、電子銃から放出された陰極線は金属銀層２上に直接ぶつかり、陰極線はまず金属銀層２を透過して、ひいては発光ガラス基板１を励起して発光させた。
Example 1
The size is 1 × 1 cm 2 and 30Li 2 O · 6Y 2 O 3 · 60SiO 2 · 4Tb 2 O 3 green light emitting glass obtained by the above preparation method of surface polishing is selected as a substrate (the numbers before each oxide are A metal silver layer having a thickness of 2 nm was deposited on the surface thereof by a magnetron sputtering apparatus, and then placed in an environment with a degree of vacuum of less than 1 × 10 −3 Pa. After annealing at a temperature of 30 ° C. for 30 minutes, it was cooled to room temperature to obtain a light emitting glass element in this example. As shown in FIG. 1, this is a structural diagram of a light-emitting glass element, and the light-emitting glass element in this example has a light-emitting glass substrate 1 as a substrate and a metal layer provided thereon. The silver layer 2 was selected, and the cathode rays emitted from the electron gun collided directly on the metallic silver layer 2. The cathode rays first transmitted through the metallic silver layer 2 and thus excited the luminescent glass substrate 1 to emit light.
電子銃から発生した陰極線は本実施例のガラス発光素子にぶつかり、図２に示す発光スペクトルを生じるものであって、図中の曲線１１は金属銀層が設けられていないガラスの発光スペクトルであり、曲線１２は本実施例で得られた発光ガラス素子の発光スペクトルであって、金属銀層２と発光ガラス基板１との間に表面プラズモン現象が発生しており、図中から分かるように、金属銀層２が設けられていない発光ガラスに比べて、本発明の発光ガラス素子は４００ｎｍから６５０ｎｍの発光積分強度が６．５倍にまで高められ、極めて高い発光性能が得られている。 The cathode ray generated from the electron gun collides with the glass light emitting device of this example, and generates the emission spectrum shown in FIG. 2, and the curve 11 in the figure is the emission spectrum of the glass not provided with the metallic silver layer. Curve 12 is the emission spectrum of the light-emitting glass element obtained in this example, and surface plasmon phenomenon occurs between the metallic silver layer 2 and the light-emitting glass substrate 1, and as can be seen from the figure, Compared with the luminescent glass in which the metallic silver layer 2 is not provided, the luminescent glass element of the present invention has an emission integrated intensity of 400 to 650 nm increased to 6.5 times, and extremely high luminescent performance is obtained.
実施例２
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる３０Ｌｉ２Ｏ・６Ｙ２Ｏ３・６０ＳｉＯ２・４Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、マグネトロンスパッタリング装置でその表面に厚さ８ｎｍの金属銀層を堆積させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、３００℃の温度で３０分間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 2
A green light emitting glass having a size of 1 × 1 cm 2 and 30Li 2 O · 6Y 2 O 3 · 60SiO 2 · 4Tb 2 O 3 obtained by the above-described preparation method for surface polishing is selected as a substrate, and the surface is thickened by a magnetron sputtering apparatus. A metal silver layer having a thickness of 8 nm is deposited, and then placed in an environment with a degree of vacuum of less than 1 × 10 −3 Pa, annealed at a temperature of 300 ° C. for 30 minutes, and then cooled to room temperature. The luminescent glass element in the example was obtained.
電子銃から発生した陰極線は本発明のガラス発光素子にぶつかり、図３に示す発光スペクトルを生じるものであって、図中の曲線１１は金属銀層が設けられていないガラスの発光スペクトルであり、曲線１３は本実施例で得られた発光ガラス素子の発光スペクトルであって、金属銀層２と発光ガラス基板１との間に表面プラズモン現象が発生しており、図中から分かるように、金属銀層２が設けられていない発光ガラスに比べて、本発明の発光ガラス素子は４００ｎｍから６５０ｎｍの発光積分強度が５倍にまで高められ、極めて高い発光性能が得られている。以下、各実施例の発光スペクトルはいずれも実施例１および実施例２と似ており、各発光ガラス素子も似た効果を備えることから、以下では別段説明しない。 The cathode ray generated from the electron gun collides with the glass light-emitting element of the present invention, and produces the emission spectrum shown in FIG. 3, and the curve 11 in the figure is the emission spectrum of the glass not provided with the metallic silver layer, A curve 13 is an emission spectrum of the light emitting glass element obtained in this example, and a surface plasmon phenomenon occurs between the metallic silver layer 2 and the light emitting glass substrate 1, and as can be seen from the figure, Compared with the luminescent glass in which the silver layer 2 is not provided, the luminescent glass element of the present invention has an emission integrated intensity from 400 nm to 650 nm increased to 5 times, and an extremely high luminous performance is obtained. Hereinafter, the emission spectrum of each example is similar to that of Example 1 and Example 2, and each light-emitting glass element has a similar effect, and thus will not be described below.
実施例３
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる２５Ｎａ２Ｏ・１５Ｙ２Ｏ３・４５ＳｉＯ２・１０Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、マグネトロンスパッタリング装置でその表面に厚さ０．５ｎｍの金属金層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、２００℃の温度で１時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 3
Size of 1 × 1 cm 2, green light emission glass 25Na 2 O · 15Y 2 O 3 · 45SiO 2 · 10Tb 2 O 3 obtained by the above preparation method of surface polishing is selected as a substrate, the thickness on the surface thereof by the magnetron sputtering apparatus A metal gold layer having a thickness of 0.5 nm is deposited, and then placed in an environment having a degree of vacuum of less than 1 × 10 −3 Pa, annealed at a temperature of 200 ° C. for 1 hour, and then cooled to room temperature. A light emitting glass element in this example was obtained.
実施例４
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる２７Ｎａ２Ｏ・０．０１Ｙ２Ｏ３・７０ＳｉＯ２・１５Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、マグネトロンスパッタリング装置でその表面に厚さ２００ｎｍの金属アルミニウム層を堆積させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、５００℃の温度で５時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 4
A green light emitting glass having a size of 1 × 1 cm 2 and 27Na 2 O · 0.01Y 2 O 3 · 70SiO 2 · 15Tb 2 O 3 obtained by the above-described preparation method for surface polishing is selected as a substrate, and the surface thereof is selected with a magnetron sputtering apparatus. A metal aluminum layer having a thickness of 200 nm is deposited on the substrate, and then placed in an environment having a degree of vacuum of less than 1 × 10 −3 Pa, annealed at a temperature of 500 ° C. for 5 hours, and then cooled to room temperature. A light emitting glass element in this example was obtained.
実施例５
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる３２Ｎａ２Ｏ・１．５Ｙ２Ｏ３・６５ＳｉＯ２・１２Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に厚さ１００ｎｍの金属マグネシウム層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、６５０℃の温度で５分間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 5
Size selects 1 × 1 cm 2, green light emission glass 32Na 2 O · 1.5Y 2 O 3 · 65SiO 2 · 12Tb 2 O 3 obtained by the above preparation method of surface polishing as the substrate, the electron beam vapor deposition apparatus A metal magnesium layer having a thickness of 100 nm is deposited on the surface, and then placed in an environment with a degree of vacuum of less than 1 × 10 −3 Pa, annealed at a temperature of 650 ° C. for 5 minutes, and then cooled to room temperature. The luminescent glass element in this example was obtained.
実施例６
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる３５Ｎａ２Ｏ・０．５Ｙ２Ｏ３・５０ＳｉＯ２・１３Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に厚さ１ｎｍの金属パラジウム層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、１００℃の温度で３時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 6
A green light emitting glass having a size of 1 × 1 cm 2 and 35Na 2 O · 0.5Y 2 O 3 · 50SiO 2 · 13Tb 2 O 3 obtained by the above preparation method of surface polishing is selected as a substrate, and the electron beam evaporation apparatus A metal palladium layer having a thickness of 1 nm was deposited on the surface, and then placed in an environment with a degree of vacuum of less than 1 × 10 −3 Pa, annealed at a temperature of 100 ° C. for 3 hours, and then cooled to room temperature. The luminescent glass element in this example was obtained.
実施例７
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる３８Ｎａ２Ｏ・１２Ｙ２Ｏ３・４３ＳｉＯ２・０．５Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に厚さ５ｎｍの金属白金層を堆積させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、４５０℃の温度で１５分間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 7
The size is 1 × 1 cm 2 , and 38Na 2 O · 12Y 2 O 3 · 43SiO 2 · 0.5Tb 2 O 3 green light emitting glass obtained by the above preparation method of surface polishing is selected as a substrate, and the electron beam evaporation apparatus A metal platinum layer having a thickness of 5 nm was deposited on the surface, and then placed in an environment with a degree of vacuum of less than 1 × 10 −3 Pa, annealed at a temperature of 450 ° C. for 15 minutes, and then cooled to room temperature. The luminescent glass element in this example was obtained.
実施例８
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる２８Ｎａ２Ｏ・１０Ｙ２Ｏ３・６８ＳｉＯ２・２Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に厚さ２０ｎｍの金属鉄層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、５０℃の温度で５時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 8
A green light emitting glass having a size of 1 × 1 cm 2 and 28Na 2 O · 10Y 2 O 3 · 68SiO 2 · 2Tb 2 O 3 obtained by the above-described preparation method for surface polishing is selected as a substrate, and the surface thereof is applied by an electron beam evaporation apparatus. A metal iron layer having a thickness of 20 nm is deposited, and then placed in an environment with a degree of vacuum of less than 1 × 10 −3 Pa, annealed at a temperature of 50 ° C. for 5 hours, and then cooled to room temperature. The luminescent glass element in an Example was obtained.
実施例９
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる３５Ｋ２Ｏ・８Ｙ２Ｏ３・５５ＳｉＯ２・０．０１Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に厚さ１０ｎｍの金属チタン層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、１５０℃の温度で２時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 9
A green light emitting glass having a size of 1 × 1 cm 2 and 35K 2 O · 8Y 2 O 3 · 55SiO 2 · 0.01Tb 2 O 3 obtained by the above preparation method of surface polishing is selected as a substrate, and the electron beam evaporation apparatus A titanium metal layer having a thickness of 10 nm is deposited on the surface, and then placed in an environment with a degree of vacuum of less than 1 × 10 −3 Pa, annealed at a temperature of 150 ° C. for 2 hours, and then cooled to room temperature. The luminescent glass element in this example was obtained.
実施例１０
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる４０Ｋ２Ｏ・５Ｙ２Ｏ３・４０ＳｉＯ２・９Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に厚さ５０ｎｍの金属銅層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、２００℃の温度で２．５時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 10
A green light emitting glass having a size of 1 × 1 cm 2 and 40K 2 O · 5Y 2 O 3 · 40SiO 2 · 9Tb 2 O 3 obtained by the above-described preparation method for surface polishing is selected as a substrate, and the surface thereof is applied by an electron beam evaporation apparatus. A metal copper layer with a thickness of 50 nm was deposited, and then placed in an environment where the degree of vacuum was less than 1 × 10 −3 Pa, annealed at a temperature of 200 ° C. for 2.5 hours, and then cooled to room temperature. The luminescent glass element in this example was obtained.
実施例１１
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる３６Ｋ２Ｏ・８Ｙ２Ｏ３・５８ＳｉＯ２・０．８Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に厚さ１５０ｎｍの金属亜鉛層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、３５０℃の温度で０．５時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 11
A green light emitting glass having a size of 1 × 1 cm 2 and 36K 2 O · 8Y 2 O 3 · 58SiO 2 · 0.8Tb 2 O 3 obtained by the above preparation method of surface polishing is selected as a substrate, and the electron beam evaporation apparatus A metal zinc layer having a thickness of 150 nm is deposited on the surface, and then placed in an environment where the degree of vacuum is less than 1 × 10 −3 Pa, annealed at a temperature of 350 ° C. for 0.5 hours, and then cooled to room temperature. Thus, a light emitting glass element in this example was obtained.
実施例１２
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる２９Ｋ２Ｏ・１１Ｙ２Ｏ３・５０ＳｉＯ２・１．５Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に厚さ１２０ｎｍの金属クロム層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、２５０℃の温度で２時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 12
A green light emitting glass having a size of 1 × 1 cm 2 and 29K 2 O · 11Y 2 O 3 · 50SiO 2 · 1.5Tb 2 O 3 obtained by the above preparation method of surface polishing is selected as a substrate, and the electron beam evaporation apparatus A metal chromium layer having a thickness of 120 nm was deposited on the surface, and then placed in an environment where the degree of vacuum was less than 1 × 10 −3 Pa, annealed at a temperature of 250 ° C. for 2 hours, and then cooled to room temperature. The luminescent glass element in this example was obtained.
実施例１３
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる３３Ｋ２Ｏ・７Ｙ２Ｏ３・５８ＳｉＯ２・７Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に厚さ４０ｎｍの金属ニッケル層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、８０℃の温度で４時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 13
A green light emitting glass having a size of 1 × 1 cm 2 and 33K 2 O · 7Y 2 O 3 · 58SiO 2 · 7Tb 2 O 3 obtained by the above-described preparation method for surface polishing is selected as a substrate, and the surface thereof is applied by an electron beam evaporation apparatus. A metal nickel layer having a thickness of 40 nm is deposited, and then placed in an environment having a degree of vacuum of less than 1 × 10 −3 Pa, annealed at a temperature of 80 ° C. for 4 hours, cooled to room temperature, The luminescent glass element in an Example was obtained.
実施例１４
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られる２６Ｋ２Ｏ・４Ｙ２Ｏ３・６９ＳｉＯ２・９．５Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に厚さ１８０ｎｍの金属コバルト層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、４００℃の温度で１時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 14
The size is 1 × 1 cm 2 and 26K 2 O · 4Y 2 O 3 · 69SiO 2 · 9.5Tb 2 O 3 green light emitting glass obtained by the above-mentioned preparation method of surface polishing is selected as a substrate, and the electron beam evaporation apparatus A metallic cobalt layer having a thickness of 180 nm is deposited on the surface, and then placed in an environment with a degree of vacuum of less than 1 × 10 −3 Pa, annealed at a temperature of 400 ° C. for 1 hour, and then cooled to room temperature. The luminescent glass element in this example was obtained.
実施例１５
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られ４５Ｋ２Ｏ・８Ｙ２Ｏ３・４８ＳｉＯ２・１．５Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に８ｎｍの金属層中の銀とアルミニウムと重量割合がそれぞれ８０％と２０％である金属銀・アルミニウム層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、３８０℃の温度で２．５時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 15
Size selects 1 × 1 cm 2, green light emission glass obtained 45K 2 O · 8Y 2 O 3 · 48SiO 2 · 1.5Tb 2 O 3 by the above preparation method of surface polishing as the substrate, the electron beam vapor deposition apparatus On the surface, silver and aluminum in a metal layer of 8 nm and a metal silver / aluminum layer having a weight ratio of 80% and 20%, respectively, are deposited, and then placed in an environment where the degree of vacuum is less than 1 × 10 −3 Pa. After annealing at a temperature of 380 ° C. for 2.5 hours, it was cooled to room temperature to obtain a light emitting glass element in this example.
実施例１６
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られ３６Ｋ２Ｏ・１６Ｙ２Ｏ３・５２ＳｉＯ２・４Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に１５ｎｍの金属層中の銀とアルミニウムと重量割合がそれぞれ９０％と１０％である金属銀・アルミニウム層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、１８０℃の温度で３．５時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 16
A green light emitting glass having a size of 1 × 1 cm 2 and obtained by the above-described preparation method for surface polishing is selected as a substrate and green light emitting glass of 36K 2 O · 16Y 2 O 3 · 52SiO 2 · 4Tb 2 O 3 is selected on the surface by an electron beam evaporation apparatus. A metal silver / aluminum layer having a weight ratio of 90% and 10%, respectively, is deposited on the 15 nm metal layer, and then placed in an environment with a degree of vacuum of less than 1 × 10 −3 Pa. After annealing at a temperature of 3.5 ° C. for 3.5 hours, it was cooled to room temperature to obtain a light emitting glass element in this example.
実施例１７
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られ５５Ｋ２Ｏ・３Ｙ２Ｏ３・６２ＳｉＯ２・７Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に７ｎｍの金属層中の金とアルミニウムと重量割合がそれぞれ８０％と２０％である金属金・アルミニウム層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、２７０℃の温度で１．５時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 17
A green light emitting glass having a size of 1 × 1 cm 2 and 55K 2 O · 3Y 2 O 3 · 62SiO 2 · 7Tb 2 O 3 obtained by the above-described preparation method for surface polishing is selected as a substrate, and the surface thereof is applied by an electron beam evaporation apparatus. A metal gold / aluminum layer having a weight ratio of 80% and 20%, respectively, was deposited on a 7 nm metal layer, which was then placed in an environment with a vacuum of less than 1 × 10 −3 Pa. After annealing at a temperature of 1.5 ° C. for 1.5 hours, it was cooled to room temperature to obtain a light emitting glass element in this example.
実施例１８
サイズが１×１ｃｍ２、表面研磨の上記調製方法により得られ５８Ｋ２Ｏ・６Ｙ２Ｏ３・３５ＳｉＯ２・９Ｔｂ２Ｏ３の緑色発光ガラスを基板として選択し、電子ビーム蒸着装置でその表面に８０ｎｍの金属層中の金とアルミニウムと重量割合がそれぞれ９０％と１０％である金属金・アルミニウム層を蒸着させ、その後これを真空度が１×１０−３Ｐａ未満の環境下に置き、６００℃の温度で４．５時間アニール処理した後、室温にまで冷却して、本実施例における発光ガラス素子を得た。
Example 18
Size of 1 × 1 cm 2, green light emission glass obtained 58K 2 O · 6Y 2 O 3 · 35SiO 2 · 9Tb 2 O 3 by the above preparation method of surface polishing is selected as a substrate, on the surface by electron beam evaporation device A metal gold / aluminum layer having a weight ratio of 90% and 10%, respectively, was deposited on the 80 nm metal layer, and then placed in an environment where the degree of vacuum was less than 1 × 10 −3 Pa, 600 After annealing at a temperature of 4.5 ° C. for 4.5 hours, it was cooled to room temperature to obtain a light emitting glass element in this example.
Claims (12)
式中、Ｍはアルカリ金属元素であり、ａ、ｂ、ｃ、ｄはモル分率であり、これらの値の範囲が、ａは２５〜６０、ｂは０．０１〜１５、ｃは４０〜７０、ｄは０．０１〜１５である、ことを特徴とする電界放出発光材料の発光効率を高める方法に用いられる発光ガラス素子。 A light-emitting glass element used in a method for increasing luminous efficiency of a field emission light-emitting material provided with a light-emitting glass substrate, wherein a metal layer is provided on a surface of the light-emitting glass substrate, and the metal layer has a metal microstructure. has, the light emitting glass substrate includes a composite oxide of formula aM 2 O · bY 2 O 3 · cSiO 2 · dTb 2 O 3,
In the formula, M is an alkali metal element, a, b, c, and d are mole fractions, and the ranges of these values are as follows: a is 25 to 60, b is 0.01 to 15, and c is 40 to 40. 70 and d are 0.01 to 15, wherein the light emitting glass element is used in a method for increasing the light emission efficiency of a field emission light emitting material.
化学式がａＭ２Ｏ・ｂＹ２Ｏ３・ｃＳｉＯ２・ｄＴｂ２Ｏ３であって、式中、Ｍはアルカリ金属元素であり、ａ、ｂ、ｃ、ｄはモル分率であり、これらの値の範囲が、ａは２５〜６０、ｂは０．０１〜１５、ｃは４０〜７０、ｄは０．０１〜１５である複合酸化物を含む発光ガラス基板を調製する工程と、
前記発光ガラス基板の表面に金属層を形成する工程と、
前記発光ガラス基板および金属層に真空にてアニール処理して、前記金属層に金属微細構造を形成して、冷却した後に所望の発光ガラス素子を得る工程と、を含む、ことを特徴とする発光ガラス素子の調製方法。 A method for preparing a light emitting glass element, comprising:
Formula is a aM 2 O · bY 2 O 3 · cSiO 2 · dTb 2 O 3, wherein, M is an alkali metal element, a, b, c, d are mole fractions, these values Wherein a is 25 to 60, b is 0.01 to 15, c is 40 to 70, and d is 0.01 to 15;
Forming a metal layer on the surface of the light emitting glass substrate;
And a step of annealing the light emitting glass substrate and the metal layer in a vacuum to form a metal microstructure in the metal layer and cooling to obtain a desired light emitting glass element. A method for preparing a glass element.
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| PCT/CN2009/072403 WO2010148553A1 (en) | 2009-06-23 | 2009-06-23 | Method for raising luminous efficiency of field emissive luminescent material, luminescent glass element and the preparing method thereof |
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| WO2018163759A1 (en) * | 2017-03-09 | 2018-09-13 | 日本電気硝子株式会社 | Glass material and method for manufacturing same |
| JP2018150222A (en) * | 2017-03-09 | 2018-09-27 | 日本電気硝子株式会社 | Glass material and method for producing the same |
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| EP2489644B1 (en) * | 2009-08-26 | 2018-12-19 | Ocean's King Lighting Science&Technology Co., Ltd. | Luminescent element, producing method thereof and luminescence method using the same |
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| CN102422384A (en) | 2012-04-18 |
| WO2010148553A1 (en) | 2010-12-29 |
| EP2447982A4 (en) | 2016-11-30 |
| US9087685B2 (en) | 2015-07-21 |
| CN102422384B (en) | 2013-09-18 |
| EP2447982A1 (en) | 2012-05-02 |
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| US20120077025A1 (en) | 2012-03-29 |
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